EP3667777B1 - Matière active d'électrode négative, électrode négative comprenant cette matière, et batterie secondaire comprenant l'électrode négative - Google Patents

Matière active d'électrode négative, électrode négative comprenant cette matière, et batterie secondaire comprenant l'électrode négative Download PDF

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EP3667777B1
EP3667777B1 EP18854257.5A EP18854257A EP3667777B1 EP 3667777 B1 EP3667777 B1 EP 3667777B1 EP 18854257 A EP18854257 A EP 18854257A EP 3667777 B1 EP3667777 B1 EP 3667777B1
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Prior art keywords
negative electrode
active material
electrode active
particle
coating layer
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German (de)
English (en)
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EP3667777A2 (fr
EP3667777A4 (fr
Inventor
Jung Hyun Choi
So Ra Lee
Eun Kyung Kim
Yong Ju Lee
Sun Young Shin
Hyeon Min Song
Jee Eun Kim
Seo Young Kwon
Il Geun Oh
Jae Young Lee
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LG Energy Solution Ltd
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LG Energy Solution Ltd
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/362—Composites
    • H01M4/366—Composites as layered products
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/131—Electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/133—Electrodes based on carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/134—Electrodes based on metals, Si or alloys
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/362—Composites
    • H01M4/364—Composites as mixtures
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
    • H01M4/386—Silicon or alloys based on silicon
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/483—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides for non-aqueous cells
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/485—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • H01M4/587—Carbonaceous material, e.g. graphite-intercalation compounds or CFx for inserting or intercalating light metals
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/624—Electric conductive fillers
    • H01M4/625—Carbon or graphite
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M2004/021—Physical characteristics, e.g. porosity, surface area
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
    • H01M2004/027—Negative electrodes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
    • H01M2004/028—Positive electrodes
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Definitions

  • the present invention relates to a negative electrode active material, a negative electrode including the negative electrode active material, and a secondary battery including the negative electrode, wherein, specifically, the negative electrode active material includes a carbonaceous matrix including a fist particle and a second particle, the first particle includes a silicon core; an oxide layer which is disposed on the silicon core and includes SiO x (0 ⁇ x ⁇ 2), and lithium silicate; and a coating layer which covers at least a portion of a surface of the oxide layer and includes LiF, and the second particle is flaky graphite.
  • an electrochemical device using the electrochemical energy may be a secondary battery and there is a trend that its usage area is expanding more and more.
  • demand for secondary batteries as an energy source has been significantly increased as technology development and demand with respect to portable devices, such as portable computers, mobile phones, and cameras, have increased.
  • lithium secondary batteries having high energy density, i.e., high capacity have been subjected to considerable research and have been commercialized and widely used.
  • a secondary battery is composed of a positive electrode, a negative electrode, an electrolyte, and a separator.
  • the negative electrode includes a negative electrode active material in which lithium ions from the positive electrode are intercalated and deintercalated, and silicon-based particles having high discharge capacity may be used as the negative electrode active material.
  • the silicon-based particle such as SiO x (0 ⁇ x ⁇ 2), has low initial efficiency and its volume is excessively changed during charge and discharge. Thus, there is a limitation in that lifetime of the battery is reduced.
  • US 20160365567 relates to silicon/graphite/carbon composites, to a method for producing them, and to their use as electrode active material in lithium ion batteries.
  • LiF lithium fluoride
  • SEI solid electrolyte interface
  • US 20170117543 relates to a negative electrode active material particle and a method for preparing the same.
  • An aspect of the present invention provides a negative electrode active material, which may effectively control changes in volume during charge and discharge of a secondary battery and a side reaction with an electrolyte solution, a negative electrode including the same, and a secondary battery including the negative electrode.
  • a negative electrode active material which includes a carbonaceous matrix including a fist particle and a second particle, wherein the first particle includes a silicon core; an oxide layer which is disposed on the silicon core and includes SiO x (0 ⁇ x ⁇ 2), and lithium silicate; and a coating layer which covers at least a portion of a surface of the oxide layer and includes LiF, and the second particle is flaky graphite.
  • a negative electrode including the negative electrode active material and a secondary battery including the negative electrode.
  • initial efficiency and discharge capacity of a battery may be improved by a coating layer including LiF, and an electrode thickness change rate may be reduced. Also, since compositing of first particles and second particles may be smoothly performed by flaky graphite, capacity retention may be improved and the electrode thickness change rate may be further reduced.
  • a negative electrode active material 100 includes a carbonaceous matrix 130 including a fist particle 110 and a second particle 120, wherein the first particle 110 includes a silicon core 111; an oxide layer 112 which is disposed on the silicon core 111 and includes SiO x (0 ⁇ x ⁇ 2); and a coating layer 113 which covers at least a portion of a surface of the oxide layer and includes LiF, and the second particle 120 may be flaky graphite.
  • the silicon core may include silicon (Si), and, specifically, may be formed of Si. Accordingly, capacity of a secondary battery may be increased.
  • An average particle diameter (D 50 ) of the silicon core may be in a range of 40 nm to 400 nm, particularly 60 nm to 200 nm, and more particularly 80 nm to 150 nm. In a case in which the average particle diameter satisfies the above range, the nano-sized silicon core does not break easily during charge and discharge of the battery and intercalation and deintercalation of lithium may be effectively performed.
  • the average particle diameter (D 50 ) may be defined as a particle diameter at 50% in the cumulative particle diameter distribution.
  • the average particle diameter (D 50 ), for example, may be measured by using a laser diffraction method.
  • the laser diffraction method may generally measure a particle diameter ranging from a submicron level to a few mm and may obtain highly repeatable and high-resolution results.
  • the oxide layer may be disposed on the silicon core. Specifically, the oxide layer may cover at least a portion of a surface of the silicon core.
  • the oxide layer includes SiO x (0 ⁇ x ⁇ 2) and Lithium silicate, and may specifically include SiO 2 . Accordingly, an excessive change in volume of the silicon core may be controlled during charge and discharge of the secondary battery.
  • the oxide layer may have a thickness of 0.01 nm to 20 nm, particularly 0.05 nm to 15 nm, and more particularly 0.1 nm to 10 nm. In a case in which the thickness satisfies the above range, the excessive change in volume of the silicon core may be effectively controlled while the capacity of the secondary battery is maintained.
  • the coating layer may cover at least a portion of the surface of the oxide layer. Specifically, the coating layer may be disposed to cover the entire surface of the oxide layer or may be disposed to cover the portion of the surface.
  • the coating layer may include LiF, and, specifically, may be composed of LiF. Since the LiF of the coating layer may act as a kind of a solid electrolyte interface (SEI), a side reaction of the silicon core with an electrolyte solution may be prevented, lithium ion conductivity may be improved, and the excessive change in volume of the silicon core may be controlled. Accordingly, initial efficiency of a negative electrode may be improved. Specifically, although the present invention is not limited thereto, the LiF included in the coating layer may be composed of a crystalline phase and an amorphous phase due to a heat treatment that is applied during the preparation of the negative electrode active material. In this case, the lithium ion conductivity may be improved due to an interface between the crystalline phase and the amorphous phase.
  • SEI solid electrolyte interface
  • the coating layer may be included in an amount of 0.05 wt% to 25 wt%, particularly 0.1 wt% to 20 wt%, and more particularly 0.5 wt% to 15 wt% based on a total weight of the negative electrode active material.
  • the amount of the coating layer satisfies the above range, the side reaction of the silicon core with the electrolyte solution may be effectively prevented, the lithium ion conductivity may be effectively improved, and the excessive change in volume of the silicon core may be effectively controlled. Accordingly, the initial efficiency of the negative electrode may be effectively improved.
  • the coating layer may have a thickness of 0.01 nm to 50 nm, particularly 0.05 nm to 15 nm, and more particularly 0.1 nm to 10 nm. In a case in which the thickness of the coating layer satisfies the above range, the above-described effect of the coating layer may be further improved.
  • the oxide layer further includes lithium silicate.
  • the lithium silicate may be formed when the oxide layer and the coating layer, which are in an appropriate ratio, are heat-treated at a predetermined heat treatment temperature during the formation of the carbonaceous matrix. That is, the lithium silicate may be a byproduct formed by reaction of the LiF with the oxide layer. Since initial irreversible capacity of the battery may be reduced by the lithium silicate, initial efficiency of the battery may be improved.
  • the lithium silicate may include at least one of Li 2 SiO 3 , Li 4 SiO 4 , and Li 2 Si 2 O 5 , and may specifically include Li 2 SiO 3 .
  • the second particle may be flaky graphite.
  • the flaky graphite may be at least one selected from natural graphite, artificial graphite, and graphite-based particles prepared by pulverizing natural graphite or artificial graphite. Since the second particle is included in the negative electrode active material, a conductive path may be secured in an active material layer. Furthermore, when compared with spherical graphite, since the flaky graphite has a plate shape, the first particle and the second particle may be aggregated with higher density in a process of compositing the first particle and the second particle. Thus, energy density of the prepared negative electrode may be improved, a thinner electrode may be prepared, and battery resistance may be reduced.
  • the flaky graphite may have a Brunauer-Emmett-Teller (BET) specific surface area of 1 m 2 /g to 200 m 2 /g, particularly 1.5 m 2 /g to 100 m 2 /g, and more particularly 2 m 2 /g to 50 m 2 /g.
  • BET Brunauer-Emmett-Teller
  • a weight ratio of the first particle to the second particle may be in a range of 1:9 to 9:1, particularly 2:8 to 8:2, and more particularly 4:6 to 7:3. In a case in which the weight ratio is satisfied, since the first particle and the second particle may be stably composited simultaneously with an improvement in the capacity of the battery, stability of the battery may be improved.
  • the negative electrode active material may include a structure in which the first particle and the second particle are composited by being in contact with each other.
  • the carbonaceous matrix may be present in the form of covering at least a portion of the first particle and the second particle, and, specifically, the carbonaceous matrix may be present in the form of covering all of the first particle and the second particle.
  • the carbonaceous matrix may include at least one of amorphous carbon and crystalline carbon.
  • the crystalline carbon may further improve conductivity of the negative electrode active material.
  • the crystalline carbon may include at least one selected from the group consisting of fullerene, carbon nanotubes, and graphene.
  • the amorphous carbon may suppress the expansion of the silicon core by appropriately maintaining strength of the carbonaceous matrix.
  • the amorphous carbon may include at least one carbide selected from the group consisting of tar, pitch and other organic materials or may include a carbon-based material formed by using hydrocarbon as a source of chemical vapor deposition.
  • the carbides of the other organic materials may include carbides of organic materials selected from sucrose, glucose, galactose, fructose, lactose, mannose, ribose, aldohexose, ketohexose, and combinations thereof.
  • the hydrocarbon may be a substituted or unsubstituted aliphatic or alicyclic hydrocarbon, or a substituted or unsubstituted aromatic hydrocarbon.
  • Aliphatic or alicyclic hydrocarbon of the substituted or unsubstituted aliphatic or alicyclic hydrocarbon may include methane, etherin, ethylene, acetylene, propane, butane, butene, pentane, isobutane, or hexane.
  • Aromatic hydrocarbon of the substituted or unsubstituted aromatic hydrocarbon may include benzene, toluene, xylene, styrene, ethylbenzene, diphenylmethane, naphthalene, phenol, cresol, nitrobenzene, chlorobenzene, indene, coumarone, pyridine, anthracene, or phenanthrene.
  • the carbonaceous matrix may be included in an amount of 5 wt% to 50 wt%, particularly 10 wt% to 45 wt%, and more particularly 12 wt% to 40 wt% based on the total weight of the negative electrode active material.
  • the amount of the carbonaceous matrix satisfies the above range, the conductive path may be effectively secured.
  • the carbonaceous matrix may effectively maintain bonding of the first particle and the second particle, the volume expansion of the negative electrode active material may be effectively controlled.
  • a method of preparing a negative electrode active material according to another embodiment of the present invention may include: preparing a silicon core having a surface on which an oxide layer including SiO x (0 ⁇ x ⁇ 2) is disposed; preparing a first particle by forming a coating layer including LiF on the oxide layer; and forming a carbonaceous matrix including a particle in which the first particle and a second particle, as flaky graphite, are composited.
  • the oxide layer may be formed by heat treating the silicon core in oxygen or air, or the oxide layer may be formed on the silicon core by a milling process.
  • the present invention is not necessarily limited thereto.
  • the coating layer may be formed by the following method.
  • the coating layer may be formed by the method in which the silicon core having the oxide layer formed on the surface thereof is ground and mixed by milling with LiF.
  • the coting layer may be formed by mixing lithium acetate and ammonium fluoride with the dispersed solution.
  • the coating layer may be formed by disposing LiF on the oxide layer through sputtering.
  • the present invention is not necessarily limited to the above method.
  • the forming of the carbonaceous matrix may include the following method.
  • the second particles and pitch or an organic solution which may be a carbon source, are dispersed in the mixed solution to prepare a slurry.
  • the carbonaceous matrix may be formed by heat treating and then grinding the slurry, and compositing may be achieved at the same time.
  • the slurry is subjected to spray drying and then grinding to form the carbonaceous matrix, and compositing may be achieved at the same time.
  • the carbonaceous matrix may be formed on a surface of the secondary particle by using chemical vapor deposition (CVD) or by carbonizing after being mixed with an organic material such as pitch.
  • CVD chemical vapor deposition
  • the present invention is not necessarily limited to the above method.
  • a negative electrode according to another embodiment of the present invention may include a negative electrode active material, and, herein, the negative electrode active material is the same as the negative electrode active material of the above-described embodiments.
  • the negative electrode may include a current collector and a negative electrode active material layer disposed on the current collector.
  • the negative electrode active material layer may include the negative electrode active material.
  • the negative electrode active material layer may further include a binder and/or a conductive agent.
  • the current collector is not particularly limited as long as it has conductivity without causing adverse chemical changes in the battery.
  • copper, stainless steel, aluminum, nickel, titanium, fired carbon, or aluminum or stainless steel that is surface-treated with one of carbon, nickel, titanium, silver, or the like may be used as the current collector.
  • a transition metal that adsorbs carbon well, such as copper or nickel may be used as the current collector.
  • the current collector may have a thickness of 6 ⁇ m to 20 ⁇ m, but the thickness of the current collector is not limited thereto.
  • the binder may include at least one selected from the group consisting of a polyvinylidene fluoride-hexafluoropropylene copolymer (PVDF-co-HFP), polyvinylidene fluoride (PVDF), polyacrylonitrile, polymethylmethacrylate, polyvinyl alcohol, carboxymethylcellulose (CMC), starch, hydroxypropyl cellulose, regenerated cellulose, polyvinylpyrrolidone, tetrafluoroethylene, polyethylene, polypropylene, polyacrylate, an ethylene-propylene-diene monomer (EPDM), a sulfonated EPDM, a styrene-butadiene rubber (SBR), a fluorine rubber, polyacrylic acid, and polymers in which hydrogen thereof is substituted with lithium (Li), sodium (Na), or calcium (Ca), and may also include various copolymers thereof.
  • PVDF-co-HFP polyvinylidene fluoride-he
  • the conductive agent is not particularly limited as long as it has conductivity without causing adverse chemical changes in the battery, and, conductive materials, for example, graphite such as natural graphite and artificial graphite; carbon black such as acetylene black, Ketjen black, channel black, furnace black, lamp black, and thermal black; conductive fibers such as carbon fibers or metal fibers; conductive tubes such as carbon nanotubes; fluorocarbon; metal powder such as, aluminum powder, and nickel powder; conductive whiskers such as zinc oxide whiskers and potassium titanate whiskers; conductive metal oxide such as titanium oxide; or polyphenylene derivatives, may be used.
  • graphite such as natural graphite and artificial graphite
  • carbon black such as acetylene black, Ketjen black, channel black, furnace black, lamp black, and thermal black
  • conductive fibers such as carbon fibers or metal fibers
  • conductive tubes such as carbon nanotubes
  • fluorocarbon metal powder
  • metal powder such as, aluminum powder, and nickel powder
  • a secondary battery according to another embodiment of the present invention may include a negative electrode, a positive electrode, a separator disposed between the positive electrode and the negative electrode, and an electrolyte, and the negative electrode is the same as the above-described negative electrode. Since the negative electrode has been described above, detailed descriptions thereof will be omitted.
  • the positive electrode may include a positive electrode collector and a positive electrode active material layer which is formed on the positive electrode collector and includes a positive electrode active material.
  • the positive electrode collector is not particularly limited as long as it has conductivity without causing adverse chemical changes in the batteries, and, for example, stainless steel, aluminum, nickel, titanium, fired carbon, or aluminum or stainless steel that is surface-treated with one of carbon, nickel, titanium, or silver may be used.
  • the positive electrode collector may typically have a thickness of 3 ⁇ m to 500 ⁇ m and may have a surface with fine roughness to improve adhesion to the positive electrode active material.
  • the positive electrode collector may be used in various shapes, for example, a film, a sheet, a foil, a net, a porous body, a foam body, a non-woven fabric body, and the like.
  • the positive electrode active material may be a typically used positive electrode active material.
  • the positive electrode active material may include a layered compound, such as lithium cobalt oxide (LiCoO 2 ) or lithium nickel oxide (LiNiO 2 ), or a compound substituted with one or more transition metals; lithium iron oxides such as LiFe 3 O 4 ; lithium manganese oxides such as Li 1+c1 Mn 2-c1 O 4 (0 ⁇ c1 ⁇ 0.33), LiMnO 3 , LiMn 2 O 3 , and LiMnO 2 ; lithium copper oxide (Li 2 CuO 2 ); vanadium oxides such as LiV 3 O 8 , V 2 O 5 , and Cu 2 V 2 O 7 ; nickel (Ni)-site type lithium nickel oxide expressed by a chemical formula of LiNi 1-c2 M c2 O 2 (where M is at least one selected from the group consisting of cobalt (Co), manganese (Mn), aluminum (Al), copper (Cu), iron (Fe), magnesium (Mg
  • the positive electrode active material layer may include a positive electrode conductive agent and a positive electrode binder as well as the above-described positive electrode active material.
  • the positive electrode conductive agent is used for providing conductivity to the electrode, wherein any conductive agent may be used without particular limitation as long as it has electronic conductivity without causing adverse chemical changes in the battery.
  • the positive electrode conductive agent may be graphite such as natural graphite and artificial graphite; a carbon-based material such as carbon black, acetylene black, Ketjen black, channel black, furnace black, lamp black, thermal black, and carbon fibers; metal powder, such as copper powder, nickel powder, aluminum powder, and silver powder, or metal fibers; conductive whiskers such as zinc oxide whiskers and potassium titanate whiskers; conductive metal oxide such as titanium oxide; or conductive polymers such as polyphenylene derivatives, and one alone or a mixture of two or more thereof may be used.
  • the positive electrode binder functions to improve binding between positive electrode active material particles and adhesion between the positive electrode active material and the positive electrode collector.
  • the positive electrode binder may be polyvinylidene fluoride (PVDF), a polyvinylidene fluoride-hexafluoropropylene copolymer (PVDF-co-HEP), polyvinyl alcohol, polyacrylonitrile, carboxymethyl cellulose (CMC), starch, hydroxypropyl cellulose, regenerated cellulose, polyvinylpyrrolidone, polytetrafluoroethylene, polyethylene, polypropylene, an ethylene-propylene-diene polymer (EPDM), a sulfonated EPDM, a styrene-butadiene rubber (SBR), a fluoro rubber, or various copolymers thereof, and one alone or a mixture of two or more thereof may be used.
  • PVDF polyvinylidene fluoride
  • PVDF-co-HEP polyvin
  • the separator separates the negative electrode and the positive electrode and provides a movement path of lithium ions, wherein any separator may be used as the separator without particular limitation as long as it is typically used in a secondary battery, and particularly, a separator having high moisture-retention ability for an electrolyte as well as low resistance to the transfer of electrolyte ions may be used.
  • a porous polymer film for example, a porous polymer film prepared from a polyolefin-based polymer, such as an ethylene homopolymer, a propylene homopolymer, an ethylene/butene copolymer, an ethylene/hexene copolymer, and an ethylene/methacrylate copolymer, or a laminated structure having two or more layers thereof may be used.
  • a typical porous nonwoven fabric for example, a nonwoven fabric formed of high melting point glass fibers or polyethylene terephthalate fibers may be used.
  • a coated separator including a ceramic component or a polymer component may be used to secure heat resistance or mechanical strength, and the separator having a single layer or multilayer structure may be selectively used.
  • the electrolyte may include an organic liquid electrolyte, an inorganic liquid electrolyte, a solid polymer electrolyte, a gel-type polymer electrolyte, a solid inorganic electrolyte, or a molten-type inorganic electrolyte which may be used in the preparation of the lithium secondary battery, but the present invention is not limited thereto.
  • the electrolyte may include a non-aqueous organic solvent and a metal salt.
  • non-aqueous organic solvent may be aprotic organic solvents, such as N-methyl-2-pyrrolidone, propylene carbonate, ethylene carbonate, butylene carbonate, dimethyl carbonate, diethyl carbonate, ⁇ -butyrolactone, 1,2-dimethoxy ethane, tetrahydrofuran, 2-methyl tetrahydrofuran, dimethyl sulfoxide, 1,3-dioxolane, formamide, diemthylformamide, dioxolane, acetonitrile, nitromethane, methyl formate, methyl acetate, phosphate triester, trimethoxy methane, a dioxolane derivative, sulfolane, methyl sulfolane, 1,3-dimethyl-2-imidazolidinone, a propylene carbonate derivative, a tetrahydrofuran derivative, ether, methyl propionate, and ethyl propionate
  • an electrolyte solution having high electrical conductivity may be prepared when the ring-type carbonate is mixed with low-viscosity, low-dielectric constant linear carbonate, such as dimethyl carbonate and diethyl carbonate, in an appropriate ratio, the ring-type carbonate may be more preferably used.
  • a lithium salt may be used as the metal salt, and the lithium salt is a material that is readily soluble in the non-aqueous electrolyte solution, wherein, for example, any one selected from the group consisting of F - , Cl - , I - , NO 3 - , N(CN) 2 - , BF 4 - , CIO 4 - , PF 6 - , (CF 3 ) 2 PF 4 - , (CF 3 ) 3 PF 3 - , (CF 3 ) 4 PF 2 - , (CF 3 ) 5 PF - , (CF 3 ) 6 P - , CF 3 SO 3 - , CF 3 CF 2 SO 3 -, (CF 3 SO 2 ) 2 N - , (FSO 2 ) 2 N - , CF 3 CF 2 (CF 3 ) 2 CO - , (CF 3 SO 2 ) 2 CH - , (SF 5 ) 3 C - , (CF 3
  • At least one additive for example, a haloalkylene carbonate-based compound such as difluoroethylene carbonate, pyridine, triethylphosphite, triethanolamine, cyclic ether, ethylenediamine, n-glyme, hexamethyl phosphoric triamide, a nitrobenzene derivative, sulfur, a quinone imine dye, N-substituted oxazolidinone, N,N-substituted imidazolidine, ethylene glycol dialkyl ether, an ammonium salt, pyrrole, 2-methoxy ethanol, or aluminum trichloride, may be further included in the electrolyte in addition to the above-described electrolyte components for the purpose of improving life characteristics of the battery, preventing a decrease in battery capacity, and improving discharge capacity of the battery.
  • a haloalkylene carbonate-based compound such as difluoroethylene carbonate, pyridine, triethylphosphit
  • a battery module including the secondary battery as a unit cell and a battery pack including the battery module are provided. Since the battery module and the battery pack include the secondary battery having high capacity, high rate capability, and high cycle characteristics, the battery module and the battery pack may be used as a power source of a medium and large sized device selected from the group consisting of an electric vehicle, a hybrid electric vehicle, a plug-in hybrid electric vehicle, and a power storage system.
  • the dispersion was spray-dried under conditions including an inlet temperature of 180°C, an aspirator rate of 95%, and a feeding rate of 12 using a mini spray-dryer (manufacturer: Buchi, model: B-290 Mini Spray-Dryer). Thereafter, 10 g of the spray-dried mixture (composite) was heat-treated at 950°C in a nitrogen atmosphere to prepare a negative electrode active material.
  • An amount of LiF (corresponding to the coating layer of the present invention) in the prepared negative electrode active material was 0.8 wt% based on a total weight of the negative electrode active material, wherein the amount of LiF was a value calculated by summing an amount of Li and an amount of fluorine (F) which were measured by inductively coupled plasma (ICP) spectrometry and ion chromatography, respectively.
  • ICP inductively coupled plasma
  • a negative electrode slurry was prepared by adding 3.1 g of N-methyl-2-pyrrolidone (NMP), as a solvent, to the mixture.
  • NMP N-methyl-2-pyrrolidone
  • a 20 ⁇ m thick copper (Cu) thin film, as a negative electrode collector was coated with the negative electrode slurry and dried. In this case, a temperature of circulating air was 80°C. Subsequently, the coated negative electrode collector was roll-pressed and dried in a vacuum oven at 130°C for 12 hours to prepare a negative electrode.
  • the prepared negative electrode was used and a Li-metal thin film cut into a circle of area 1.7671 cm 2 was used as a positive electrode.
  • a porous polyethylene separator was disposed between the positive electrode and the negative electrode, and a lithium coin half-cell was prepared by injecting an electrolyte solution in which 0.5 wt% vinylene carbonate was dissolved and 1 M LiPF 6 was dissolved in a mixed solution in which a mixing volume ratio of ethyl methyl carbonate (EMC) to ethylene carbonate (EC) was 7:3.
  • EMC ethyl methyl carbonate
  • EC ethylene carbonate
  • a negative electrode active material was prepared in the same manner as in Example 1 except that LiF was not added during the preparation of the slurry in the preparation step of the negative electrode active material of Example 1.
  • a negative electrode and a secondary battery were prepared in the same manner as in Example 1 by using the negative electrode active material.
  • the dispersion was spray-dried under conditions including an inlet temperature of 180°C, an aspirator rate of 95%, and a feeding rate of 12 using a mini spray-dryer (manufacturer: Buchi, model: B-290 Mini Spray-Dryer). Thereafter, 10 g of the spray-dried mixture (composite) was heat-treated at 950°C in a nitrogen atmosphere to prepare a negative electrode active material.
  • An amount of LiF (corresponding to the coating layer of the present invention) in the prepared negative electrode active material was 0.8 wt% based on a total weight of the negative electrode active material, wherein the amount of LiF was a value calculated by summing an amount of Li and an amount of F which were measured by ICP spectrometry and ion chromatography, respectively.
  • a negative electrode and a secondary battery were prepared in the same manner as in Example 1 by using the negative electrode active material.
  • Example 1 The batteries of Example 1 and Comparative Examples 1 and 2 were charged and discharged to evaluate discharge capacity, initial efficiency, capacity retention, and electrode (negative electrode) thickness change rate, and the results thereof are listed in Table 1 below.
  • the batteries were charged and discharged at 0.1 C, and charging and discharging were performed at 0.5 C from a 3 rd cycle to a 49 th cycle.
  • a 50 th cycle was terminated in a charged state (state in which lithium was included in the negative electrode), the battery was disassembled to measure a thickness, and the electrode thickness change rate was then calculated.
  • the discharge capacity (mAh/g) and the initial efficiency (%) were derived from the results during the first charge and discharge cycle. Specifically, the initial efficiency (%) was derived by the following calculation.
  • Initial efficiency % discharge capacity after the 1 st discharge / 1 st charge capacity ⁇ 100
  • Example 1 With respect to Example 1, it may be understood that discharge capacity, initial efficiency, capacity retention, and electrode thickness change rate were all better than those of Comparative Examples 1 and 2. With respect to Comparative Example 1, since the negative electrode active material did not include LiF, a conductive path was not secured, and thus, the initial efficiency and the discharge capacity seemed to be reduced. In addition, with respect to Example 1, since lithium silicate (Li 2 SiO 3 ) , which was formed from LiF and SiO 2 , may be present in the negative electrode active material, it seems that the initial efficiency and the discharge capacity may be further improved in comparison to those of Comparative Example 1 in which the lithium silicate was not present (see FIG. 3 ). With respect to Comparative Example 2, since the spherical natural graphite was used, compositing of the first particle and the second particle was not stably performed, and thus, it may be understood that the capacity retention and the electrode thickness change rate were poor.
  • Li 2 SiO 3 lithium silicate

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Claims (12)

  1. Matériau actif d'électrode négative comprenant :
    une matrice carbonée incluant une première particule et une seconde particule,
    dans lequel la première particule comprend un noyau de silicium ;
    une couche d'oxyde qui est disposée sur le noyau de silicium et inclut du SiOx (0 < x ≤ 2) et du silicate de lithium ; et
    une couche de revêtement qui recouvre au moins une portion d'une surface de la couche d'oxyde et inclut du LiF,
    la seconde particule est du graphite floconneux.
  2. Matériau actif d'électrode négative selon la revendication 1, dans lequel le noyau de silicium présente un diamètre de particule moyen (D50) de 40 nm à 400 nm, mesuré en utilisant un procédé de diffraction laser.
  3. Matériau actif d'électrode négative selon la revendication 1, dans lequel la couche d'oxyde présente une épaisseur de 0,01 nm à 20 nm.
  4. Matériau actif d'électrode négative selon la revendication 1, dans lequel la couche de revêtement est incluse en une quantité de 0,05 % en poids à 25 % en poids sur la base d'un poids total du matériau actif d'électrode négative.
  5. Matériau actif d'électrode négative selon la revendication 1, dans lequel la couche de revêtement présente une épaisseur de 0,01 nm à 50 nm.
  6. Matériau actif d'électrode négative selon la revendication 1, dans lequel le graphite floconneux présente une surface spécifique Brunauer-Emmett-Teller (BET) de 1 m2/g à 200 m2/g.
  7. Matériau actif d'électrode négative selon la revendication 1, dans lequel un rapport pondéral de la première particule sur la seconde particule est dans une plage de 1 : 9 à 9 : 1.
  8. Matériau actif d'électrode négative selon la revendication 1, dans lequel la matrice carbonée est incluse en une quantité de 5 % en poids à 50 % en poids sur la base d'un poids total du matériau actif d'électrode négative.
  9. Matériau actif d'électrode négative selon la revendication 1, dans lequel le silicate de lithium comprend au moins l'un parmi Li2SiO3, Li4SiO4, ou Li2Si2O5.
  10. Matériau actif d'électrode négative selon la revendication 1, dans lequel la première particule et la seconde particule sont en contact l'une avec l'autre.
  11. Électrode négative comprenant le matériau actif d'électrode négative selon l'une quelconque des revendications 1 à 10.
  12. Batterie secondaire comprenant :
    l'électrode négative selon la revendication 11 ;
    une électrode positive ;
    un séparateur disposé entre l'électrode positive et l'électrode négative ; et
    un électrolyte.
EP18854257.5A 2017-09-11 2018-08-30 Matière active d'électrode négative, électrode négative comprenant cette matière, et batterie secondaire comprenant l'électrode négative Active EP3667777B1 (fr)

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KR1020170116083A KR102285979B1 (ko) 2017-09-11 2017-09-11 음극 활물질, 상기 음극 활물질을 포함하는 음극, 및 상기 음극을 포함하는 이차 전지
PCT/KR2018/010099 WO2019050216A2 (fr) 2017-09-11 2018-08-30 Matériau actif d'anode, anode comprenant ledit matériau actif d'anode et batterie secondaire comprenant ladite anode

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CN110993912A (zh) * 2019-09-25 2020-04-10 东莞赣锋电子有限公司 一种硅碳负极电池的制备
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KR102600047B1 (ko) * 2023-04-24 2023-11-08 (주)디온에너지 음극표면 코팅막 형성 방법 및 이를 적용한 리튬 1차 전지

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CN1913200B (zh) * 2006-08-22 2010-05-26 深圳市贝特瑞电子材料有限公司 锂离子电池硅碳复合负极材料及其制备方法
KR101049829B1 (ko) * 2009-10-28 2011-07-15 삼성에스디아이 주식회사 리튬 이차 전지용 음극 활물질 및 이를 포함하는 리튬 이차 전지
JP5585470B2 (ja) * 2011-01-27 2014-09-10 株式会社豊田自動織機 リチウムイオン二次電池
JP6239326B2 (ja) * 2013-09-20 2017-11-29 株式会社東芝 非水電解質二次電池用負極材料、非水電解質二次電池用負極、非水電解質二次電池及び電池パック
KR101676086B1 (ko) * 2013-09-26 2016-11-14 주식회사 엘지화학 실리콘계 음극 활물질, 이의 제조방법 및 이를 포함하는 리튬 이차전지
WO2015080203A1 (fr) * 2013-11-27 2015-06-04 三菱化学株式会社 Matière carbonée pour électrode négative de batterie rechargeable non aqueuse, électrode négative pour batterie rechargeable non aqueuse et batterie rechargeable non aqueuse
DE102014202156A1 (de) * 2014-02-06 2015-08-06 Wacker Chemie Ag Si/G/C-Komposite für Lithium-Ionen-Batterien
JP6082355B2 (ja) * 2014-02-07 2017-02-15 信越化学工業株式会社 非水電解質二次電池の負極材用の負極活物質、及び非水電解質二次電池用負極電極、並びに非水電解質二次電池
JP6397262B2 (ja) * 2014-02-07 2018-09-26 信越化学工業株式会社 非水電解質二次電池
KR101673719B1 (ko) 2014-03-28 2016-11-07 주식회사 엘지화학 리튬 이차전지용 음극활물질 및 그 제조방법
US10879531B2 (en) * 2015-10-26 2020-12-29 Lg Chem, Ltd. Negative electrode active particle and method for manufacturing the same
CN106784768A (zh) * 2017-02-04 2017-05-31 中天储能科技有限公司 一种硅碳负极复合材料的制备方法
KR20170046114A (ko) * 2017-04-17 2017-04-28 강원대학교산학협력단 리튬 이차전지용 음극 활물질, 그 제조방법 및 리튬 이차전지용 음극 활물질을 포함하는 리튬 이차전지

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US20200280059A1 (en) 2020-09-03
WO2019050216A2 (fr) 2019-03-14
WO2019050216A3 (fr) 2019-05-02
KR102285979B1 (ko) 2021-08-04
EP3667777A2 (fr) 2020-06-17
EP3667777A4 (fr) 2020-10-21
CN111095621B (zh) 2022-06-03
KR20190029044A (ko) 2019-03-20

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